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Spin State Chemistry: Modulation of Ligand pKa by Spin State Switching in a [2×2] Iron(II) Grid-Type Complex Sébastien Dhers, Abhishake Mondal, David Aguilà, Juan Ramirez, Sergi Vela, Pierre Dechambenoit, Mathieu Rouzieres, Jonathan R. Nitschke, Rodolphe Clérac, and Jean-Marie Lehn J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b03735 • Publication Date (Web): 06 Jun 2018 Downloaded from http://pubs.acs.org on June 6, 2018

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Journal of the American Chemical Society

Spin State Chemistry: Modulation of Ligand pKa by Spin State Communication Switching in a [2´2] Iron(II) Grid-Type Complex pubs.acs.org/JACS Sébastien Dhers,† Abhishake Mondal,‡,#,§ David Aguilà,‡,# Juan Ramírez,† Sergi Vela,◊ Pierre Dechambenoit,‡,# Mathieu Rouzières,‡,# Jonathan R. Nitschke,†,^ Rodolphe Clérac,*,‡,# and Jean-Marie Lehn*,† † ‡ #

Stepwise Transformation of the Molecular Building Blocks in a Porphyrin-Encapsulating CNRS, CRPP, UMR5031, F-33600 Pessac, FranceMetal−Organic Material

Laboratoire de Chimie Supramoléculaire, ISIS, Université de Strasbourg, 8 Allée Gaspard Monge, 67000 Strasbourg, France † † Univ. Bordeaux, CRPP, UMR5031, F-33600 Pessac, France Zhenjie Zhang, Lukasz Wojtas, Mohamed Eddaoudi,†,‡

and Michael J. Zaworotko*,†

§

Solid State and Structural Chemistry Unit, Indian Institute of Science, C.V. Raman Road, Bangalore-560012, India † Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, CHE205, Tampa, Florida 33620, United States ‡ Laboratoire de Chimie Quantique, 7177 CNRS-Université de Strasbourg, 1 rue BlaiseThuwal Pascal, 23955-6900, 67008 Strasbourg, France Chemical Science Program, 4700 UMR King Abdullah University of Science and Technology, Kingdom of Saudi ^ Arabia Department of Chemistry, University of Cambridge, CB2 1EW, UK ◊

S Supporting Information * Information

ray diffraction (SCXRD) are rare.16,20 Since Cd2+ in cadmium ABSTRACT: When immersed solutions containing ABSTRACT: The iron(II) [2´2] grid in complex Fe-8H has been synthesized and characterized. It undergoes spin-crossover porphyrins can be irreversibly exchanged with (SCO) Cu2+,21upon the Cu(II) cations, the microporous metal−organic material deprotonation of the hydrazine-based terpyridine-like ligand. The deprotonation patterns have been determined crystallography and possibility of selective control of PSMbyinX-ray porph@MOMs exists if P11 ([Cd ]·[Cd(C )(S)]·[S], BPT bi- of the iron(II) 1H NMR spectroscopy discussed in8relation to the spin=state centers greatly pKa different of the ligand. the MOM andwhich the influences encapsulated RS the exhibit ratesThe of 4(BPT)4and 44H36N phenyl-3,4′,5-tricarboxylate) undergoes a transformation In this work,behavior we addressed suchcharacterized a situation through synthesis of the magnetically-silent zinc(II) analogue is also reported andexchange. its (de)protonation has been to servethe as 2− of its for [Cdthe building blocks 2(COO) 6] themolecular study crystals of porph@MOM-11 (P11), Cd-sustained reference study of FeII grid complexes. DFT (MBBs) computations have also of been performed in order to investigate howa the successive into novelof the tetranuclear [Cu4Xaffects MBBs within to 2(COO) 2] behavior MOM that encapsulates CdTMPyP cations [H2TMPyP = mesodeprotonation bridging ligands the6(S) SCO the grid. form P11-Cu. The transformation occurs in single-crystal tetra(N-methyl-4-pyridyl)porphine tetratosylate]. P11 was to single-crystal fashion, and its stepwise mechanism was immersed in methanol solutions of Cd2+ and/or Cu2+ to study studied by varying the Cd2+/Cu2+ ratio of the solution in how the Cd2+/Cu2+ mole ratio impacts PSM. Scheme 1 shows which crystals of P11 were immersed. P11-16/1 (Cd in how porph@MOMs might generally undergo complete or modulation of their physico-chemical properties, due to their ionizable framework retained, Cd in encapsulated porphyrins partial metal exchange through control of the ratio of two metal n INTRODUCTION N-H sites. The final step of the synthesis of such a ditopic ligand conexchanged) and other intermediate phases were thereby ions.in the condensation reaction of one equivalent of 4,6sists The isolated search for having tunable properties is a and veryP11active andmaterials structurally characterized. P11-16/1 1 bis(hydrazino)-2-phenyl-pyrimidine with two equivalents of 2this microporosity context, special of attention to the research Cu area. retainInthe P11, has andbeen the given relatively Scheme 1. Metal Ion PSM inligand porph@MOMs: (i) Partial pyridine-carboxaldehyde to yield H2L. This ligand containsPSM two modulation of magnetic properties by physical suchexpansion as temperalarger MBBs in P11-Cu permit a 20%means unit cell with Metal 2 in the Presence of Both Metal 1 and 2the (Bottom 2 2,3 complexation subunits of terpyridine (terpy) type, where hydrature, and pressure light, surface or through processes affecting affordand a higher areachemical and a larger pore size. the Left); (ii) Complete Exchange with Metal 2 (Bottom Right)

ligand field in complexes.4 Spin crossover (SCO) complexes are interesting candidates, particularly iron(II) complexes, which exhibit a switching process between a paramagnetic high spin state S = 2) orous metal−organic materials (MOMs) that (HS, incorporate 1 gridand a diamagnetic low spin statesuch (LS, Sas= metalloporphyrins, 0).5 Polymetallic [2´2] reactive6 species (RS) metal2 3 like complexes modulable properties be seen as molecular losalens, andwith polyoxometalates are ofcan topical interest because 4 to precursors metallosupramolecular architectures or materials they can of combine the physicochemical properties of the RSdue with 5 their ability to generate ordered arrangements of multiple grid entities permanent porosity of the framework. 7Such MOMs can thereby 7 hydrogen-bond byenable self-assembly at the air-water separations, luminesnew approaches to gasinterface, storage,6through 8array8 and on adsorption onto a8bgraphite surformation in the solid cence, and catalysis, including enzymatic catalysis. MOMs that 9 face. It has been tetranuclear iron(II) [2´2] those grids undergo incorporate RSshown can bethat divided into two subgroups: with RS 9 multiple spin statepart switching under the action of three physical triggers, as an integral of nodes/linkers (RSMOMs) and those that 2,10 temperature, pressure and light. The influence of10hydrogen-bond encapsulate or host RS in cages (RS@MOMs). Encapsulation 11 12 11 well as directly that of counterions and solvent, also been donors, may be as achieved through synthesis or viahave postsynthetic 12 shown to allow the modulation of the magnetism of these architecmodification (PSM). Metalloporphyrins are attractive RS 13presenting ionizable 14 tures. On the other hand, [2´2] grids N-H sites because of their value as catalysts and dyes, and we recently undergo reversible protonic modulation of optical and redox properreported the generation of porphyrin-encapsulating MOMs 13 15 that the magnetic properties of such entities ties. One thus expects (porph@MOMs) that exhibit PSM through metal ion may also be16modulated ligand 17 deprotonation withoutof exchange or metal by saltreversible incorporation. The availability 2,13 destruction of the initial complex. The hydrazine-based ditopic such porph@MOMs offers the opportunity to study their PSM isomeric ligand Hand 2L (Scheme 1) offers the opportunity to both genersystematically evaluate its impact on their properties such as ategas [2´2] grid architectures by self-assembly andIntoaddition, study the PSM protonic sorption, luminescence, and catalysis. can

P

zone function acts as an ionizable group whose acidity is greatly enhanced on complexation, as compared to the free ligands.

Scheme 1. Synthesis of the ditopic ionizable hydrazine-based ligand H2L and its self-assembly into the corresponding tetranuclear [Fe4(H2L)4]8+ [2´2] grid complex by coordination with FeII cations. Red spheres represent Fe metal ions. Hydrogen atoms that are colored in blue emphasize the deprotonation sites on the [2´2] grid.

The reaction of biphenyl-3,4′,5-tricarboxylic acid (H3BPT)22 and Cd(NO3)2 with H2TMPyP afforded P11, a microporous MOM in which encapsulated cationic porphyrins occupy alternating channels.17 P11 is based upon a 3,6-connected rtl afford new compounds that cannot be directly synthesized. net built from two 6-connected [Cd2(COO)6]2− MBBs [Figure PSM involving metal exchange in molecular building blocks 1a and Figure S1 in the Supporting Information (SI)]. As (MBBs) is now widely studied and tends to focus upon Cd- and ACS Paragon Plus Environment illustrated in Figure S1, one MBB is a distorted paddlewheel Zn-containing MOMs18 because of the relative lability of 10 2+ 2+ 2+ 19 formed by seven-coordinate Cd2+ and the other is a more regular complexes of d ions (Cd , Zn , and Hg ). The metal exchange process is typically monitored using atomic absorption

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The iron(II) [2´2] grid [Fe4(H2L)4]8+ shown in Scheme 1 incorporates hydrazone groups, which act as soft ligands to assemble the iron(II) ions. The deprotonation of this two-site ligand H2L14 changes its coordination properties from a weak-field ligand (nondeprotonated) to a strong-field ligand (deprotonated). Its deprotonation also confers to the ligand an anionic15 character (-N--N=CH-, Scheme S1) thus leading to a stronger coordination with a larger splitting energy between the eg and t2g levels of the iron cations. In this configuration, all the electrons should be paired in the t2g level leading to a diamagnetic [Fe4L4] complex. However, given that a grid complex contains four FeII cations, the spin crossover process may be more or less complete depending on the strength of the ligand field. This modulation of the magnetic properties is expected to depend on the degree of deprotonation of the grid, which contains a total of eight ionizable groups. Indeed, the influence of pH on iron(II) SCO complexes has been investigated mostly in the context of NMR contrast agents16 and only a few pH switchable iron(II) SCO complexes have been reported just for single iron(II) sites.17 Herein, we describe the synthesis of the iron(II) [2´2] grid complex, [Fe4(H2L)4]8+, and the study of the reversible modulation of its magnetic properties in the solid state and solutions depending on the protonation state of the four constituting ligands. We also demonstrate the remarkable effect of the iron(II) spin state switching on the pKa of the grid ligands, which induces the generation of selectively deprotonated magnetic entities and amounts conversely to a spin state modulated chemical reaction. The zinc(II) analogue is also reported and serves as a diamagnetic reference compound for the investigation of the iron(II) grid entities.

n RESULTS AND DISCUSSION Synthesis of the ligand and of the corresponding FeII [2´2] grid complexes. Several [2´2] grids, [Fe4(HnL4)](n)+ (0 > n > 8, Fe-nH), were prepared and isolated by reaction of the corresponding ligand H2L with Fe(BF4)2 in a 1:1 molar ratio at room temperature in acetonitrile and in the case of n < 8, adding the corresponding amount of base (triethylamine) for deprotonation (see supporting information for detailed procedures). Subsequently, crystals of the [2´2] grid complexes in different states of ionization were obtained by slow diffusion of diethylether into the different solutions. Three single-crystal structures were determined by X-ray diffraction (see supporting information) and confirmed the expected [2´2] grid topology accompanied by 8, 6 and 4 BF4- anions, depending on the degree of deprotonation of the grids: [Fe4(H2L)4](BF4)8·xMeCN (Fe-8H, red needles, x = 2 or 6 at 290 and 120 K, respectively), [Fe4(H2L)2(HL)2](BF4)6·8MeCN (Fe-6H, red blocks) and [Fe4(HL)4](BF4)4·12MeCN (Fe-4H, red plates). Unfortunately, and despite intensive efforts, no crystals were obtained for the other deprotonated states. Two Zn-based [2´2] grids, [Zn4(HnL4)](n)+ (n = 8 and 4, Zn-8H and Zn-4H, respectively), were also prepared and isolated by reaction of the corresponding ligand with Zn(BF4)2 in a 1:1 molar ratio at room temperature in acetonitrile (in the case of n = 4, the corresponding amount of triethylamine was added). As zinc(II) is diamagnetic, the Zn-based complexes provide model systems to study the ligand behavior independently of the iron(II) SCO influence. Solid state molecular structures and spin states of the [Fe4(HnL4)](n)+ (n = 8, 6, 4) and [Zn4(HL)4](BF4)4 [2´2] grid complexes in different ionization states. (a) The red needle crystals of Fe-8H were found to lose crystallinity rapidly once outside the mother liquor. Thus, a single-crystal was mounted immersed in oil and placed in the X-ray diffractometer directly at 120 K. The crystal structure was solved in the monoclinic C2/c space group, exhibiting a molecular [2´2] grid topology with the four fully protonated ligands:

Figure 1. Ball and stick representations of the crystal structures of the [Fe4(H2L) 4](BF4) 8·2MeCN complex, Fe-8H, with non-ionized ligands (top) and the doubly deprotonated [Fe 4(H2L)2(HL) 2](BF4) 6·8MeCN complex, Fe-6H, (bottom) both at 290 K. Fe, N, C and H atoms are shown in red, blue, grey and white, respectively. All non-NH hydrogen atoms, acetonitrile and tetrafluoroborate molecules are omitted for clarity. Non-deprotonated NH sites are circled in red. [Fe4(H2L)4](BF4)8·6MeCN (Fe-8H, Table S1, and top part of Figure 1 and Figure S2). Together with the cationic complex, eight tetrafluoroborate anions ensure the electro-neutrality of the system and indicate the 8+ charge of the corresponding Fe-8H complex. In addition, acetonitrile molecules are located in the crystal lattice. The number of acetonitrile molecules (six) was derived from the electron density and void space volume calculated by PLATON. In the asymmetric unit, one of the BF4- anions is disordered across two positions, as is the phenyl group of one of the H2L ligands. Two types of iron ions, Fe1 and Fe2, were found in the asymmetric unit, both exhibiting coordination number six. The bond distances between Fe1 and the corresponding nitrogen donor atoms (1.885(9) – 2.060(7) Å, Table S3) suggest a low spin configuration. In contrast, the Fe2-N bond distances are in the range between both low and high spin configurations (1.971(7) – 2.133(7) Å, Table S3) suggesting possible spin state disorder on this site. The H2L ligands show hydrogen bonding interaction between their corresponding acidic NH protons and (i) two BF4- anions around the Fe2 site and (ii) one BF4- anion and one acetonitrile molecule around the Fe1 centers.

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The temperature of the same single crystal was then increased at 2 K min-1 up to 290 K. The collected structure was again solved in the monoclinic C2/c space group, with the same [2´2]-grid like geometry (Table S1). The complex is thus surrounded by the eight tetrafluoroborate anions, two of them being disordered. The number of acetonitrile molecules has been estimated to be two. Thus, the increase of temperature to 290 K seems to favor the loss of about four acetonitrile molecules. This desolvation effect is clearly seen in the reduction of the unit cell volume, which contracts from 11904.6(17) Å3 at 120 K to 11151(3) Å3 at 290 K (Table S1). The Fe2 site and its coordination sphere appears to be only slightly affected by the temperature change with Fe2-N bond distances ranging between 1.980(8) and 2.127(8) Å (Table 1 and Table S3). As observed at 120 K, the spin state of the Fe2 ion is thus in between LS and HS, in agreement with a possible spin state disorder on this site. On the other hand, the bond distances between the Fe1 site and the nitrogen donor atoms are much larger than at 120 K ranging between 2.081(8) and 2.196(8) Å. This modification of the Fe1 coordination site indicates clearly a spin-state switching from LS at 120 K to HS at 290 K and reveals the occurrence of a spincrossover process in Fe-8H.

Table 1. Summary of the FeII spin states as deduced from the crystallographic data at 120 and 290 K for Fe-8H, Fe-6H, and Fe-4H.

Fe1 Fe2 Fe3 Fe4

Fe-8H

Fe-6H

Fe-4H

(red needles) 120 K 290 K LS HS LS-HS LS-HS LS HS LS-HS LS-HS

(red blocks) 120 K 290 K LS LS LS-HS HS LS LS LS-HS HS

(red plates) 120 K LS LS-HS LS LS-HS

Note: the Fe3 and Fe4 sites are symmetry-equivalent to Fe1 and Fe2 in Fe-8H.

(b) Following the same procedure, a red block crystal of Fe-6H was mounted immersed in oil and placed in the X-ray diffractometer directly at 120 K. The crystal structure was collected and solved in the monoclinic P21/c space group (Table S1), exhibiting again a [2´2] grid-like complex. However, in this case, only six tetrafluoroborate anions were found in the structure, since two ligands exhibit a monodeprotonation giving the complex: [Fe4(H2L)2(HL)2](BF4)6·8MeCN (Fe-6H, bottom part of Figure 1 and Figure S3). Together with the anions, eight molecules of acetonitrile are located in the crystal lattice. At this temperature, three pyridyl moieties are significantly disordered. Similarly, one of the acetonitrile molecules is disordered across three different positions, while one of the BF4- anions shows disorder between two different positions. Each of the six acidic NH protons is interacting with a molecule of tetrafluoroborate anion, while no H-bond acceptor is located close to the two deprotonated hydrazone groups. The [2´2] grid-like complex shows four crystallographically different iron sites (Figure 1, bottom). Fe1 and Fe3 are surrounded by two coordination pockets featuring one protonated and one deprotonated hydrazone group. The bond distances between the metal ion (Fe1 and Fe3) and the donor N atoms are in the range for a low spin configuration (1.875(3) – 2.035(3) Å for Fe1, 1.872(4) – 2.063 Å for Fe3, Table S4). In contrast, the coordination pockets around the Fe2 and Fe4 site feature two NH groups. The Fe2-N and Fe4-N bond distances do not point strongly toward a specific electronic configuration (2.010 – 2.165 Å and 1.904(6) – 2.113(4) Å, respectively; Table S4), although this feature could be influenced by the disorder exhibited by the pyridyl groups surrounding these two metal ions. The same single-crystal was allowed to warm to 290 K (2 K min-1), and the structure was again collected (Table S1). While the same space group was used to solve the

structure (P21/c), the volume of the unit cell was found to be significantly larger (11437.0(8) and 11889.2(18) Å3 at 120 and 290 K, respectively). At this temperature, only one tetrafluoroborate anion was found to be disordered. The Fe-N bond distances around the two iron sites, Fe1 and Fe3, encapsulated by the coordination pocket featuring both protonated and deprotonated hydrazone group are very similar to the ones observed at 120 K, suggesting again a low spin configuration (1.871(4) – 2.043(4) Å and 1.871(4) – 2.053(4) Å for Fe1 and Fe3, respectively, Table S4). Thus, as expected, the deprotonation of the hydrazone group leads to a stronger ligand field and thus stabilizes the LS state of the coordinated iron metal ion. In contrast, the Fe-N bond distances around the Fe2 and Fe4 sites (surrounded by pockets featuring two non-deprotonated =N-NH- hydrazone groups) are now clearly in the range for a high-spin configuration (2.118(4) – 2.247(4) Å and 2.088(4) – 2.244(4) Å for Fe2 and Fe4, respectively, Table 1 and Table S4), evidencing a stabilization of the HS state at higher temperatures and suggesting the occurrence of a spin-crossover phenomena at these metal ion sites. (c) The crystals of the third type, the red plates, were also collected at 120 K and solved in the monoclinic P21/c space group (Table S2), exhibiting the same [2´2] grid topology. In this case, however, the number of tetrafluoroborate anions is reduced to four, implying the deprotonation of altogether four hydrazone sites of the grid ligands to give [Fe4(HL)4](BF4)4·12MeCN (Fe-4H, top part of Figure 2 and Figure S4). At this temperature, the four iron metal ions are crystallographically independent. One of them (Fe3) is disordered over two positions (Fe3a and Fe3b, respectively) as well as the two coordinating ligands surrounding this Fe site. The tetrafluoroborate (disordered over two positions) and acetonitrile molecules are located in the lattice void space. The number of solvent molecules was estimated from the electronic density and void space volume calculated by PLATON. Remarkably, the arrangement of the half-deprotonated ligands leads to Fe1 and Fe3 sites surrounded by two deprotonated hydrazone groups, while the pockets surrounding Fe2 and Fe4 centers feature only nondeprotonated hydrazone group. Confirming the trend observed in the previous structures, the short Fe-N bond distances for the iron metal ions within the deprotonated hydrazone environments suggest a LS configuration (1.840(7) – 2.036(5) Å, 1.882(13) – 2.206(10) Å and 1.875(13) – 2.126(12) Å for Fe1, Fe3a and Fe3b respectively, Table S5). It should be noted that the high value observed for one of the distances surrounding Fe3 ions is probably induced by the disorder observed in this metal site. In contrast, the values observed for the metal ions surrounded by coordinating pockets featuring only nondeprotonated hydrazone groups point rather to a HS configuration at 120 K (2.086(6) – 2.190(6) Å and 2.086(6) – 2.197(6) Å for Fe2 and Fe4, respectively, Table 1 and Table S5) even if at this temperature a spin state disorder on these sites is likely to be present. As expected, each NH group of the ligand interacts with one BF4- anion through hydrogen bonding. In contrast, no H-donor species were found surrounding the deprotonated hydrazone moieties. (d) The Zn-4H analogue was prepared as a reference complex by replacing iron(II) with zinc(II), in order to analyze the deprotonation pattern observed for Fe-4H. Single crystals of Zn-4H were obtained as crystalline red plates by diffusion of diethylether into the acetonitrile solution of the complex (see supporting information). The X-ray diffraction data on a single crystal were collected at 120 K and solved in the tetragonal P4/ncc group (Table S6), yielding a [2´2] grid-like complex similar to Fe-4H. The presence of four tetrafluoroborate anions confirms the half deprotonation of the four ligands wrapping the Zn-4H grid complex: [Zn4(HL)4](BF4)4·8H2O (bottom part of Figure 2 and Figure S5). The zinc [2´2] grid is geometrically more distorted than the Fe-4H analogue, but is also more crystallographically symmetrical, as the asymmetric unit contains only one ligand and one zinc center (Zn-N: 2.075 –2.261 Å). The tetrafluoroborate and



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while for Fe-6H, the temperature cannot be increased above 270 K without losing the complete reversibility. The lack of reversibility is clearly linked to the partial loss of the acetonitrile molecules during the magnetic measurements. Therefore, only perfectly reversible magnetic data corresponding to the structurally characterized materials are discussed in the following. The cT products at highest accessible temperature for Fe-8H, Fe-6H, and Fe-4H (300, 270 and 300 K) are 6.6, 4.3 and 3.6 cm3 K mol-1, respectively. These values are intermediate between the ones expected for a fully high spin [FeIIHS]4 complex (1216 cm3 K mol-1; FeIIHS: S = 2 and g » 2.0 to 2.3, Curie constant of 3-4 cm3 K mol-1) and for a diamagnetic [FeIILS]4 species (FeIILS S = 0, Curie constant of 0 cm3 K mol-1). Upon decreasing the temperature, the cT product gradually decreases reaching to a plateau below 120 K at 2.4, 1.5 and 2.6 cm3 K mol-1 for the Fe-8H, Fe-6H and Fe-4H grids, respectively. Analyzing the temperature dependence of the susceptibility, the proportions of HS FeII centers are estimated at 48, 31 and 26 % at room temperature (taking a g factor of 2.15), and as 17, 11 and 19 % at 50 K, for Fe-8H, Fe-6H and Fe-4H respectively. This behavior clearly demonstrates an incomplete SCO for these complexes that never reach a fully low spin configuration (four FeII LS sites) at low temperatures and neither a fully high spin configuration (four FeII HS sites) before desolvation/decomposition of the material at high temperature. This result is also in agreement with the crystal structure analysis (vide supra), which indicates the systematic presence of spin state disorder on the Fe2 and Fe4 sites at 120 K for the three compounds (Table 1) and the absence of a high-spin configuration at 290 K. When the tem-

Figure 2. Ball and stick representations of the crystal structures of [Fe4(HL) 4](BF 4)4·12MeCN complex, Fe-4H, (top) and [Zn 4(HL) 4](BF4) 4·8H2O complex, Zn-4H, (bottom) at 120 K. Fe, Zn, N, C and H atoms are shown in red, green, blue, grey and white, respectively. All non-NH hydrogen atoms, acetonitrile and tetrafluoroborate molecules are omitted for clarity. Non-deprotonated NH sites are circled in red. Only one position for Fe3 (Fe3a) and its corresponding donor atoms are shown. water molecules are located in the lattice. The number of solvent molecules was estimated from the electronic density and void space volume calculated by PLATON. The good refinement of the structure and its high symmetry demonstrate that the deprotonation pattern for the Zn4H grid is different from that of Fe-4H. Indeed, the four ZnII sites are surrounded by two HL ligands forming a coordination pocket with one deprotonated and one protonated hydrazone group. (e) The fully protonated ZnII4 [2´2] grid, Zn-8H, was also obtained and structurally characterized by X-ray diffraction (Table S6, Figures S6 and S7). Both ZnII grids, Zn-4H and Zn-8H, exhibit similar octahedricity values (S(Oh), see below)18 to the corresponding FeII grids (Table S7). Determination and Analysis of the Magnetic Properties of the FeII4 [2´2] Grid Complexes. Magnetic susceptibility measurements were performed for the Fe-8H, Fe-6H, and Fe-4H complexes in the temperature range of 1.85 - 300 K (Figure 3). The magnetic measurements shown in Figure 3 are reproducible below 300 K for Fe-8H and Fe-4H

Figure 3. Temperature dependence of cT product at 0.1 (between 1.85 and 50 K) and at 1 T (above 50 K) between 1.85 and 300 K for polycrystalline samples of Fe-8H, Fe-6H, and Fe-4H (where c is the magnetic susceptibility equal to M/H per mole of [2´2] Fe4 grid).


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perature is decreased below 20 K, a decrease in the cT product is also observed, indicating most likely the presence of spin-orbit coupling expected for FeII centers in an octahedral coordination sphere, and possibly intramolecular antiferromagnetic coupling between the Fe(II) through the pyrimidine groups.19 The field dependence of the magnetization for the [2´2] FeII4 grid (Figures S8-S10) has some notable characteristics: (i) the steady increase of the magnetization at low field without inflexion point (“S” shape curve) suggests the absence of significant magnetic interactions between the reminding magnetic sites; and (ii) a linear increase without clear saturation even at 1.8 K under 7 T. This high field behavior of the magnetization and the non-superimposable M vs H/T curves reveal most likely the presence of magnetic anisotropy expected for FeII HS centers. The magnetization value obtained at 1.85 K under 7 T are 1.95, 1.25 and 2.47 µB, confirms the residual presence of FeII HS ions in Fe-8H, Fe-6H and Fe-4H grid respectively. It is worth mentioning that preliminary solid-state reflectivity measurements on these three complexes indicate the absence of bulk photoactivity at 10 K and thus the impossibility to convert LS FeII centers into HS ones using light irradiation in the visible range. UV-Vis Spectroscopic Properties of the FeII4 [2´2] Grid Complexes upon Base Titration The UV-Vis spectra of the grid Fe-8H (Figure 4) were measured in acetonitrile/chloroform (1:1) on addition of increasing equivalents of bis(dimethylamino)naphthalene (DMAN) base. The grid Fe-8H exhibits an absorption band at 372 nm, which is characteristic of the fully protonated grid complex. When two equivalents of base are added to give Fe-6H, the intensity of the band at 455 nm increases but diminishes after further base addition. A third band at 543 nm appears after adding more than 2 base equivalents, increasing in intensity until reaching a maximum intensity for the fully deprotonated species Fe0H. Considering the ratio of molar absorption coefficient and the λmax obtained, and comparing it to the values known for [Fe(Hpaphy)2]2+ and [Fe(paphy)2] (Table S8, Hpaphy = pyridine-2-aldehyde-2pyridylhydrazone), these charge transfer bands observed appear to be of MLCT (Metal Ligand Charge Transfer) type.14 The deprotonation affects markedly the color of the solution (Figure 4). UV-Vis spectra have also been measured between pH = 1 and pH = 13 in a 50:50 (v/v) mixture of acetonitrile and Britton-Robinson buffer, showing similar results (Figure S11).

Figure 4. (top) UV-Vis spectra of the grid Fe-8H after progressive addition of base in acetonitrile/chloroform (1:1); (bottom) corresponding pictures of Fe-8H solution after addition of base (0 to 8 eq., left to right).

1 H NMR Spectral Studies of the FeII4 [2´2] Grid Complexes upon Acid/Base Titration. SCO phenomena have been observed in solution by 1H NMR spectroscopy for FeII4 [2´2] grid-type complexes,2a but remain scarce.2b,20 Mass spectrometry (see supporting information) was used to ensure that the species in solution were indeed the [2´2] grid structures observed in the solid state (Figures S12-S17). The titration of a solution of Fe-8H (followed by 1H NMR in CD3CN/CDCl3 (1:1) at 25°C) with successive equivalents of DMAN or proton sponge showed chemical shifts ranging from around -40 to 200 ppm, with broad signals, and a shift of the signals towards the range for diamagnetic species as more equivalents of base were added (Figure S18). The titration produced a color change of the solution, from yellow to dark red (Figure 4, bottom), as well as a change in the solubility of the Fe-nH complex. The Fe-8H grid is soluble in acetonitrile but not in chloroform, whereas the opposite is true for Fe-0H. Hence the solvent mixture CD3CN/CDCl3 (1:1) was chosen for the NMR studies. The titration was also done in pure CD3CN (0 to 4 equivalents of base, up to the solubility limit) to allow for an increase in the maximum concentration in order to give a better NMR spectrum (Figure S19). The amount of exchange present in solution, known for grid structures,13c plus the equilibrium between Fe-nH species, render complicated the observation of the paramagnetic peaks associated with the grid (Figures S18 and S19). Nevertheless, paramagnetic peaks are clearly observed for Fe-8H to Fe-4H, as expected from the crystal structures, and are in agreement with the presence of HS FeII centers in the grid complexes. The titration also follows the expected trend, going from a strongly paramagnetic species for Fe-8H to a weakly paramagnetic Fe-4H system (containing less HS FeII sites), then to LS diamagnetic Fe-2H to Fe-0H grids with no paramagnetic signal observed. The formally Fe-3H complex is the crossover species between paramagnetic and diamagnetic systems, and it is difficult to infer whether or not this species is still paramagnetic in solution. To further investigate this magnetic behavior in solution upon deprotonation, the magnetic susceptibility was determined by 1H NMR using the Evans method on the Fe-8H grid following the same titration procedure. The results obtained (Figure 5) agree completely with those qualitatively described above. The susceptibility value for Fe-8H is 0.047 cm3 mol-1 (cT = 14 cm3 K mol-1) in excellent agreement with the presence of four FeII HS (with g = 2.16). Therefore, in solution, the Fe-8H complex is, or is close to, the fully paramagnetic configuration. Progressive addition of up to 8 equivalents of DMAN produced a marked decrease of the magnetic susceptibility to 0 cm3 mol-1 between 5 and 6 equivalents of base (Figure 5). This decrease of the

Figure 5. Evolution of the magnetic susceptibility (and cT product) of Fe-nH in CD3CN/CDCl 3 (1:1) at 298 K on titration with DMAN base as observed by 1H NMR using the Evans method. Error bars represent standard deviation over 3 experiments.



susceptibility on addition of base clearly revealed a dependence of the grid magnetic configuration with a number of HS or LS FeII sites dependent upon the degree of deprotonation. Furthermore, back titration performed by adding progressively trifluoromethanesulfonic acid (CF3SO3H) resulted in a similar pattern for the magnetic susceptibility, showing the reversibility of this system upon protonation/deprotonation. This result also highlights the fully diamagnetic configuration in solution for species Fe-2H to Fe-0H. Here again it is difficult to be definitive about the magnetic state of Fe-3H, which seems to be still slightly paramagnetic but falls within the standard deviation range of diamagnetic species (Figure 5). On the other hand, the formally Fe-4H complex generated by adding four base equivalents is clearly not diamagnetic suggesting that the deprotonation of the four hydrazone groups does not lead to four LS FeII sites in agreement with the structural and magnetic measurements in solid state (Table 1). The present titration results demonstrate a reversible Proton-Driven Spin State Switching (PD-SSS) without modification of the metal ion coordination in contrast to what has been observed in the tris(bipyridine)iron(II) system which shows also a proton-driven spin state switching but induced by a change in coordination state upon protonation (PD-CISSS).17a The [2´2] grid Zn-8H was also investigated as a diamagnetic model for Fe-8H. The base chosen for this titration was triethylamine (NEt3) to make sure that the base signals would not interfere with the diamagnetic grid signals. As in the case of Fe-8H, the solubility of the grid changes with deprotonation, with Zn-8H to Zn-4H being soluble in acetonitrile (Figure S20), and Zn-3H to Zn-0H being soluble in DMSO but not in acetonitrile or chloroform (Figure S21). In contrast to the iron grid, all 1H NMR signals of Zn-8H correspond as expected to a diamagnetic species over the titration range (from 0 to 8 equivalents of base) and can be assigned by COSY NMR (Figure S22). Both Fe-4H and Zn-4H seem to be pivotal species in their respective deprotonation series, as going from the 4H to 3H protonation states shows similar changes both in solubility and color. As crystal structures only reflect the solid state and not the solution state observed by 1H NMR, control experiments have been performed. In the case of the Fe complexes, two distinct 1H NMR spectra were observed during the titration, the initial one being the same as that of a solution obtained by dissolution of Fe-8H crystals (Figures S18 and S19). After addition of 4 equivalents of base, the second distinct pattern was identified. This solution was then taken out of the NMR spectrometer and slow ether diffusion yielded crystals confirmed by XRay crystallography to be Fe-4H. To ensure that the crystals obtained were the only type present, several different crystals were tried, giving the same result. Therefore, the symmetrical deprotonation pattern observed for the Zn-4H grid (consisting of each metal ion site surrounded by two HL ligands forming a coordination pocket with one deprotonated and one non-deprotonated hydrazone group) is not observed for Fe-4H even after crystallization of the titrated solution. This result is consistent with the paramagnetic signature of the Fe-4H solution (Figure 5) as one would expect a symmetrical Fe-4H species to be fully diamagnetic with each FeII center surrounded by one deprotonated ligand environment. It is worth mentioning that Zn-4H with the symmetrical deprotonation pattern has also been reproducibly isolated from the corresponding titrated NMR solution. Computational studies on FeII grids: Magnetic Configuration Energetics and Deprotonation Patterns. In order to investigate how the successive deprotonation of the bridging ligands affects the SCO properties within the grid, DFT computations have been performed to monitor the stability of the relevant magnetic configurations depending on the deprotonation pattern. These configurations are HS with four HS FeII sites, LS with four LS FeII sites and intermediate states with two HS and two LS FeII centers either in opposite, noted IS-trans, or neighboring, noted IS-cis, sites of the grid, or with one HS and three

Page 6 of 10

LS FeII centers referred to HLLL (Table S9). Other magnetic configurations have been computed and found of little interest for the discussion. The stability is discussed only in terms of electronic enthalpies (𝐻"#"$ ) due to the difficulty to evaluate the vibrational enthalpy (𝐻%&' ) and entropy (𝑆%&' ) contributions. The 𝐻"#"$ values for relevant magnetic configurations and deprotonation patterns of Fe-8H, Fe-6H, Fe4H and Fe-3H are given in Table S9. To evaluate the magnetic configuration stability at a given temperature from our calculations and allow a direct comparison with experiment, we have assumed 𝛥𝐻%&' = −3 kJ/mol, and 𝛥𝑆*+* = 35 J/K·mol, which lie in the common range of values, and a Boltzmann distribution of states based on free enthalpies (𝛥𝐺 = 𝛥𝐻"#"$ + 𝛥𝐻%&' − 𝑇𝛥𝑆*+* ). The computational model consists of an isolated [2´2] grid, whose structure is optimized at different magnetic configurations to obtain 𝐻"#"$ . Deviations from experimental measurements can be ascribed to crystal packing effects originated in the interactions with counterions, solvent molecules or other grids. These effects could be incorporated to our computational analysis by means of solid-state calculations with periodic boundary conditions. However, the size of the unit cells (ca. 1000 atoms) makes such analysis extremely expensive in the present case. The calculations for the Fe-8H complex indicate a HS ground configuration with a less stable LS state lying at about 21.1 kJ/mol (see Table S9), and also a IS-trans state that is slightly preferred over the IS-cis one (7.3 and 8.9 kJ/mol above HS, respectively). One of the reasons for the disfavored LS structure in the calculations is found by looking at the FeII coordination spheres. Indeed, most of the LS FeII centers in the structurally characterized grids (shown in Tables 2 and S7) have octahedricity values within the range 2.24-2.46 indicating a slightly distorted octahedral geometry.17,22 In contrast, the LS configuration for Fe8H has a significantly-larger calculated S(Oh) value (ca. 2.60; Table S10) indicating that the Fe coordination sphere should be more distorted and, thus, disfavored. In the case of the Fe-6H complex, three deprotonation patterns have been explored: a single deprotonation of two different Fe centers in (i) cis and (ii) trans positions within the grid, or (iii) a double deprotonation in one center (i.e. homo). The results show that such homo pattern is clearly unfavorable with respect to the cis and trans ones, both showing similar stability. In light of these calculations, it is difficult to suggest which might be the most stable structure at room temperature, since multiple configurations should be thermally accessible. To illustrate the complexity, assuming the aforementioned 𝛥𝐻%&' and 𝛥𝑆*+* values, there would be four states with more than 5% population at 300 K, and the ratio of HS:IS:LS states would be ca. 1:1:0. This is in line with the poorly-defined 1H NMR spectrum following the addition of two equivalents of base as observed in Figures S18 and S19, indicative of a superposition of multiple proton-transfer isomers. Similarly, at 120 K the ratio of HS:IS:LS states would be of ca. 1:9:0. For Fe-4H, we have explored two deprotonation patterns in which only one proton is removed from each of the four FeII centers (so-called hetero) or two protons are removed from the same two FeII centers (i.e. homo). In contrast with the results discussed for Fe-6H, the homo pattern is far more stable than the hetero one for all of the explored magnetic configurations. Concerning the stability, the LS configuration is the most stable one in terms of 𝐻"#"$ , but the IS-trans lies very close in energy (1.0 kJ/mol) so it is likely thermally populated at moderate temperatures due to the favorable entropic contribution. Indeed, assuming the same 𝛥𝐻%&' and 𝛥𝑆*+* values as before, we would obtain a population of 93% of the IS-trans state at 120 K with the homo deprotonation pattern, which would be consistent with the crystallographic data (Table 1). Finally, for Fe-3H we have performed a less systematic study, whose purpose has been to evaluate (i) the preference for the homo deprotonation over the hetero one, and (ii) the possibility of accessible paramagnetic configurations. The two points are confirmed by our calculations; the hetero configu-


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Table 2. Calculated octahedricity parameters: S(Oh) values18,22 as a measure of distortion of the Fe-N6 coordination sphere for 1 to 4 SCO centers in selected grids. Values of S(Oh) smaller than 4.42 indicate a geometry closer to the octahedron than to the trigonal prism, while S(Oh) values above 4.42 point toward a distorted trigonal prism geometry.18,22 Deprotonation

Fe-8H

Fe-6H-Trans

Fe-6H-Cis

Fe-6H-Homo

Fe-4H-Homo

① ② ③ ④ Avg.

6.44 6.51 6.58 6.46 6.50

6.47 6.77 6.75 6.46 6.61

6.36 7.07 7.09 6.50 6.76

6.45 6.58 6.91 6.48 6.61

6.61 6.58 6.53 6.62 6.58

① ② ③ ④ Avg.

2.58 2.60 2.60 2.58 2.59

2.39 2.41 2.45 2.42 2.42

2.45 2.45 2.38 2.40 2.42

2.40 2.42 2.39 2.40 2.40

2.32 2.41 2.44 2.28 2.36

HS

S(Oh)

LS

S(Oh)

ration lies 8 kJ/mol above the homo one, and the HLLL state is accessible since it is only 1.3 kJ/mol higher than the LS state, which means that at room temperature one would have 70% of HLLL state. These results are also in good agreement with the experimental data shown in Figure 5. Overall, the calculations clearly over-stabilize the HS configuration for the Fe-8H grid (8+ charge), and to some extent also for the Fe-6H grids (6+ charge). In turn, the HS/LS stability in the Fe-4H grids (4+ charge) seems to be better balanced. The origin for such decreasing error as we reduce the intrinsic charge of the grid might be associated to the decrease of the intermolecular interactions between the grids and their neighbors (either counterions, lattice-solvent molecules or other grids). Indeed, these interactions might have an important electrostatic contribution that is missing in our calculations, whose importance must certainly decrease along with the deprotonation. If this contribution were stabilizing the LS state (or penalizing the HS state), then the apparent errors in the mixed HS/LS state stability could be certainly ascribed to the absence of such electrostatic interactions in our computational model. Nevertheless, the deprotonation patterns observed by crystallography are supported by the present calculations, with the first two deprotonation steps (Fe-8H to Fe-6H) occurring in opposite sides of the grid (i.e. hetero) and the third and fourth steps (Fe-6H to Fe-4H) occurring in the already-deprotonated sites (i.e. homo). Additional pKa calculations have also been performed on a truncated version of an isolated FeII center (see supporting information). The numerical results show that the HS FeII center has a higher pKa value than the LS site (Table S11). Overall the unexpected unsymmetrical deprotonation pattern seen in Fe-4H seems to be induced by the intramolecular cooperativity enforced by the ligands, as has been shown for similar FeII [2´2] grids, both experimentally and theoretically.12a,21 This effect can be monitored by Continuous Shape Measurements (CShM), which evaluate the octahedricity of the Fe-N6 coordination sphere, i.e. its distortion from an ideal octahedron (S(Oh) = 0),18,22 and enable us to gain some relevant insight concerning the mutual influence between the FeII centers in the studied grid (Table 2). First, the deprotonation of one coordination pocket not only affects the

S(Oh) value of the Fe metal ion in that pocket but affects also the two neighboring Fe centers coordinated to the two ligands of the deprotonated coordination pocket and, indirectly, the whole grid. This is precisely what is expected from a system displaying intramolecular cooperativity, and can be illustrated, for instance, in the S(Oh) values of the HS configuration for the Fe-6H-Cis deprotonation pattern, in which the largest value corresponds to an Fe pocket that is not deprotonated (7.09, Table 2). This is surprising at first sight, but can be understood by looking at the actual structure of the grid, which presents a significant degree of distortion that stems from the Fe-N6 coordination sphere but is absorbed by the whole grid. As a result of this observation and for the sake of simplicity, our discussion in the next paragraph will be based on S(Oh) values averaged for the four Fe sites of the grid (see Avg. values in Tables 2 and S10). Indeed, the deprotonation affects differently the HS and LS FeII centers. The S(Oh) value of HS centers increases from Fe-8H (6.50) to Fe-6H (6.61 for homo and trans, and 6.76 for cis) and then decreases from Fe-6H to Fe-4H (6.58). On the contrary, the S(Oh) value of the LS centers continuously decrease upon deprotonation from Fe-8H (2.59) to Fe-6H (2.42 for trans and cis, and 2.40 for homo) to Fe-4H (2.36) (Tables 2 and S10). This observation indicates that the coordination pockets of the ligand are better suited to coordinate a LS FeII metal ion after deprotonation, whereas the opposite trend holds for a HS center. Making the fair assumption that, the larger the distortion of the Fe-N6 sphere, the larger the energy penalty, it would explain the progressive (de)stabilization of (HS)LS centers upon deprotonation that is captured in Table S9. Of course, the scenario is significantly more complex for IS and HLLL configurations so we have restricted our analysis to states in which all Fe centers are either HS or LS (Table S10). Even though other energy contributions are likely to contribute to the HS/LS relative stability, this analysis provides a microscopic interpretation to the magnetic configuration stability of the reported [2´2] grid. Modulation of the magnetic configuration in the [Fe4(HnL4)](n)+ (n = 4, 6, 8) complexes as a function of protonation state in light of



the structural, magnetic and computational data. Remarkably, on reaching the conditions for deprotonation of four of the eight hydrazone N-H sites belonging to the four ligands of the [Fe4(H2L)4]8+ complex (Fe-8H), the crystal structure of the corresponding complex [Fe4(HL4)]4+ (Fe-4H) showed that a double deprotonation had occurred at two FeII metal centers (Figure 2, top), the other two coordination centers remaining fully protonated. This result is in strong contrast with an expected symmetrical pattern of single deprotonation on each of the four coordination sites, as it is indeed observed in the crystal structure of the zinc analogue Zn-4H (Figure 2, bottom). Indeed, it was shown that for complexes of a ligand such as Hpaphy (Scheme 2), the pKa increases after the first ligand deprotonation.14 An estimation of the acidity of the N-H site for Hpaphy gives pKa = 14.5.23 In the [FeII(Hpaphy)2]2+ complex, the N-H site becomes much more acidic, due to the binding of the doubly charged metal cation (pKa1 = 5.68). The second deprotonation occurs at a higher pKa2 of 6.57 in aqueous solution (Scheme 2).14 These values offer an approximation of what one would expect for the iron(II) sites of the Fe-8H grid. Interestingly both [Fe(Hpaphy)2]2+ and [Fe(paphy)2] species are diamagnetic complexes.24

Scheme 2. Acidity constants pKa of [Fe(Hpaphy)2]2+ (left), [Fe(Hpaphy)(paphy)]+ (middle) and Hpaphy (right).

Page 8 of 10

must be higher than the pKa2 of the two LS iron centers that underwent SCO. The stability of this unsymmetrical deprotonation pattern for Fe-4H is well supported by the calculations on both grid stability and influence of FeII spin state on pKa (Tables 2 and S11).

n CONCLUSIONS

The data presented herein demonstrate the possibility of modulating the spin state of the FeII sites and subsequently the magnetic properties of a [2´2] FeII grid-like complex by variation of the degree of deprotonation of the hydrazine-based N-H sites of the ligand in the complex. Evidence has been provided, both in the solid state and in solution, towards understanding the strong influence of the spin-crossover process on the pKas of the grid ligands, which exhibit a unique depro† † †,‡ tonation pattern. present study providesMohamed a demonstration of the Zhenjie Zhang,The Lukasz Wojtas, Eddaoudi, and M effect of spin state switching of a chemical property, here on ligand pKa † Department of Chemistry,grid. University of South Florida, 4202 East Fowler Aven in a metallosupramolecular

Stepwise Transformation of the Molecular Porphyrin-Encapsulating Metal−Organic M ‡

Chemical Science Program, 4700 King Abdullah University of Science and Tec ■ ASSOCIATED CONTENT Arabia S Supporting Information * Supporting Information

The Supporting Information is available free of charge on the ACS Publications website at DOI: ABSTRACT: When immersed in solutions containing Experimental details about syntheses, crystal structures, physical Cu(II) cations, the microporous metal−organic material and theoretical calculations (PDF) P11 characterizations ([Cd4(BPT)4]·[Cd(C H N )(S)]·[S], BPT = bi44 36 8 X-ray crystallographic dataundergoes for Fe-8H a(120 and 290 K ; CIF), phenyl-3,4′,5-tricarboxylate) transformation 2−290 K ; CIF), Fe-4H (120 K ; CIF), Zn-8H Fe-6H (120 and of its [Cd2(COO)6] molecular building blocks (MBBs) CIF) and Zn-4H K ; CIF) (S) ] MBBs to into (173 novelK ;tetranuclear [Cu(120 X (COO) 4 2

As stated above, Fe-8H exhibits a very unusual deprotonation behavior. As for paphy complexes, two different pKas would be expected on the same metal center, pKa1(H2L/HL) and pKa2(HL/L), leading to the deprotonation pattern indeed observed for Zn-4H. The proposed explanation for the different deprotonation patterns observed for Fe4H and Zn-4H is that the FeII spin state switching from HS to LS affects the pKa of the corresponding N-H ligand site to a point that the pKa2(HL/L) of an LS coordination center becomes lower than the pKa1(H2L/HL) of a HS site. Following this reasoning, Fe-6H then also exhibits an interesting deprotonation pattern, as in that case a trans deprotonation is observed involving two different, diagonally located FeII centers – as opposed to the removal of both protons on the same metal site. This cooperative effect between FeII centers due to ligand rigidity within iron(II) [2´2] grids has been evidenced before for multi-step spin crossover processes, both experimentally and theoretically.12a,21 These results show that the SCO is facilitated first between FeII from opposite corners but then hampered for further spin state switching. The experimental and theoretical data on our system lead us to similar conclusion on the importance of cooperativity and ligand rigidity in a grid complex, as evidenced by the CShM calculations (Table S10). DFT calculations also showed clearly that for a same ligand system, the pKa is lower for a LS FeII site than it is for the HS analogue (Table S11). Relating the results of the calculations to the behavior of our system, the first double deprotonation step (Fe-8H to Fe-6H), rather than resulting from the influence of the FeII spin state on the ligand pKa, is governed by the rigidity of the ligand which forces a deprotonation on two different sites. The second double deprotonation step (Fe-6H to Fe-4H) is in turn governed by the change in pKa induced by the SCO of the trans-located iron centers, now in the LS state. The reason is that the pKa1 of the two remaining HS iron centers

6

2

form P11-Cu. The transformation occurs in single-crystal ■ INFORMATION to AUTHOR single-crystal fashion, and its stepwise mechanism was studied by varying the Cd2+/Cu2+ ratio of the solution in Corresponding Authors which crystals of P11 were immersed. P11-16/1 (Cd in *framework [email protected] retained, Cd in encapsulated porphyrins *exchanged) [email protected] and other intermediate phases were thereby ORCID isolated and structurally characterized. P11-16/1 and P11Sébastien Dhers: Cu retain the 0000-0001-5530-0818 microporosity of P11, and the relatively Abhishake Mondal: 0000-0002-5061-2326 larger MBBs in P11-Cu permit a 20% unit cell expansion David Aguilà:a 0000-0001-8707-7833 and afford higher surface area and a larger pore size.

ray diffracti porphyrins possibility o the MOM exchange. In study of cr MOM that tetra(N-me immersed in how the Cd how porph partial meta ions.

Scheme 1. M with Metal Left); (ii) C

Juan Ramirez: 0000-0003-2254-5813 Sergi Vela: 0000-0002-3431-2470 Pierre Dechambenoit: 0000-0001-7850-2260 orous metal−organic materials (MOMs) that incorporate Jonathan R. Nitschke: 0000-0002-4060-5122 reactive species (RS) such as metalloporphyrins,1 metalRodolphe Clérac: 0000-0001-5429-7418 losalens,2 and polyoxometalates3 are of topical interest because Jean-Marie Lehn: 0000-0001-8981-4593 4

P

they can combine the physicochemical properties of the RS with permanent porosity of the framework.5 Such MOMs can thereby Notes enable new approaches to gas storage,6 separations,7 luminesThe authors declare no competing financial interests. cence, and catalysis,8 including enzymatic catalysis.8b MOMs that incorporate RS can be divided into two subgroups: those with RS ■ ACKNOWLEDGMENTS as an integral part of nodes/linkers (RSMOMs)9 and those that 10 encapsulate hostERC RS in(Advanced cages (RS@MOMs). Encapsulation We thank orthe Research Grant SUPRADAPT 11 may be achieved directly through synthesis or via postsynthetic 290585), the University of Strasbourg, the University of Bordeaux, the 12 modification (PSM). Metalloporphyrins attractive RS Région Nouvelle Aquitaine, the CNRS, the GdRare MCM-2: Magnétisme 13 14 because of their value as catalystsand and and we recently thedyes, MOLSPIN COST action et Commutation Moléculaires reported MOMs of CA15128the for generation funding. S.V.of isporphyrin-encapsulating thankful to the LabEx-Chemistry 15 Complex Systems for post-doctoral grant (ANR-10-LABX(porph@MOMs) that a exhibit PSM through metal ion 16 17 0026CSC) or andmetal to the salt regional High-Performance exchange incorporation. TheComputing availability(HPC) of center in Strasbourg for computational resources. J.M.L. thanks such porph@MOMs offers the opportunity to study their PSMJack Harrowfield and Stadler for discussions. systematically andMihail evaluate its impact on their properties such as gas sorption, luminescence, and catalysis. In addition, PSM can ■ REFERENCES afford new compounds that cannot be directly synthesized. PSM involving metal exchange in molecular building blocks (1) (a) Kahn, O.; Martinez, C. J. Science 1998, 279, 44-48. (b) Gat(MBBs) is now widely studied and tends to focus upon Cd- and teschi, D.; Sessoli, R.; Villain, 18 F. Molecular Nanomagnets, Oxford University Zn-containing MOMs because of the relative lability of Press: Oxford, U.K., 2006. (c) Li, J.-R.; Kuppler, R. J.; Zhou, H.-C. Chem. complexes of d10 ions (Cd2+, Zn2+, and Hg2+).19 The metal exchange process is typically monitored using atomic absorption spectroscopy (AAS) and powder X-ray diffraction (PXRD), and ACS Paragon Plusexamples Environment where PSM has been followed using single-crystal X© 2013 American Chemical Society

5982

The react and Cd(NO MOM in alternating net built fro 1a and Fig illustrated i formed by s Received: Published:

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